CN102702102A - Method for preventing hydroxylamine in inorganic liquid from decomposing in process of preparing caprolactam - Google Patents
Method for preventing hydroxylamine in inorganic liquid from decomposing in process of preparing caprolactam Download PDFInfo
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- CN102702102A CN102702102A CN2012101780707A CN201210178070A CN102702102A CN 102702102 A CN102702102 A CN 102702102A CN 2012101780707 A CN2012101780707 A CN 2012101780707A CN 201210178070 A CN201210178070 A CN 201210178070A CN 102702102 A CN102702102 A CN 102702102A
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- azanol
- nitrous gases
- mist eliminator
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Abstract
The invention discloses a method for preventing hydroxylamine in inorganic liquid from decomposing in the process of preparing caprolactam. According to the method, nitric acid is trapped by using a demister above the top of a nitrous gas absorption tower in the processes of ammoxidation and nitrous gas absorption of a device for preparing the caprolactam; the nitric acid trapped by the demister is introduced below the liquid level of reaction liquid of the bottom of the nitrous gas absorption tower; and the liquid level in the demister is controlled automatically by an inverted U-shaped tube arranged at a liquid-phase outlet of the demister, wherein the height of the topmost position of the inverted U-shaped tube is 0.45 to 0.65 time the height of the liquid-phase part of the demister, and the position of the demister is 1 to 3 meters higher than the top of the nitrous gas absorption tower. According to the method, a process is simple and reasonable, low in cost, energy-saving and environment-friendly and has excellent economic and social benefits, and the problem of the decomposition of the hydroxylamine in the inorganic liquid of the caprolactam prepared by a hydroxylamine phosphate method fundamentally is solved.
Description
Technical field
The present invention relates to the preparation field of hexanolactam, be specifically related to a kind of hydroxylamine phosphate legal system that prevents and be equipped with the method that azanol decomposes in the inorganic liquid of hexanolactam.
Background technology
The hydroxylamine phosphate method is claimed the HPO method again, is the hydroxylammonium salt preparation method of the external invention seventies in last century, and China introduces the end of the eighties in last century, is applied in the preparation process of hexanolactam.The preparation of hydroxylamine phosphate is at noble metal catalyst platinum/palladium/charcoal (p
t/ p
d/ c) or palladium/charcoal (p
d/ c) exist down, be in the inorganic process liquor of buffer medium at phosphoric acid, prepare hydroxylamine phosphate with the hydrogen reducing nitrate radical.Temperature of reaction is 50 ~ 60 ℃, and pressure is 2550 ~ 2650K
Pa, PH is 1.8 ~ 2.2.Reaction equation is following:
Main reaction NO
3 -+ 2H
++ 3H
2=NH
3OH
++ 2H
2O
Side reaction NO
3 -+ 2H
++ 4H
2=NH
4 ++ 3H
2O
2NO
3 -+2H
++5H
2＝N
2+6H
2O
2NO
3 －+2H
++4H
2＝N
2O+5H
2O
The hydroxylamine phosphate legal system is equipped with caprolactam technology and roughly is divided into four operations, i.e. azanol synthesis procedure, oxime synthesis procedure, inorganic process liquor cleaning procedure and ammonia oxidation and nitrous gases (NO
X) the absorption operation.The azanol synthesis procedure makes the hydroxylamine phosphate solution of 0.7 ~ 0.9mol/kg, gets into the oxime synthesis procedure.Hydroxylamine phosphate solution generates oxime at oxime synthesis procedure and reactive ketone, behind the separation of organic substances, contains ammonium salt, phosphoric acid and a small amount of organic inorganic process liquor and gets into inorganic liquor cleaning procedure.Inorganic liquid gets into ammonia oxidation and nitrous gases and absorbs operation after extraction, stripping purifying treatment remove organism and part moisture.Inorganic liquid ammonia oxidation and nitrous gases absorb operation absorb nitrous gases replenish nitrate ion and divide take off unnecessary ammonium radical ion after, after removing the nitrous gases of carrying secretly, get into the azanol synthesis procedure again and recycle.This shows in the preparation process of hydroxylamine phosphate; Inorganic process liquor is that operation recycles continuously; The inorganic liquid that recycles in the azanol tower intake chute contains the azanol of 0.04 ~ 0.07mol/kg; This part azanol is often owing to absorb the nitric acid that captures when operation removes nitrous gases at ammonia oxidation and nitrous gases and import, and makes local H
+Ion is excessive; Or scurrying into of nitrous gases causes that azanol decomposes, and causes serious consequence.The decomposition of this part azanol is a chain reaction, takes place in case that is to say decomposition, and azanol in the azanol tower intake chute and the azanol in the follow-up charging thereof will all divide to be taken off.This part azanol accounts for 5 ~ 10% of azanol quality total amount, promptly produces load and also will descend 5 ~ 10%.This not only has a strong impact on the throughput of auto levelizer, has also increased material consumption and energy consumption greatly, even the material handling that stops of having to, and causes heavy economic losses.
This shows that do not produce ammonium sulfate though the hydroxylamine phosphate legal system is equipped with caprolactam technology at the oxime synthesis procedure, the quality of caprolactam of production is good, how to solve the problem that azanol decomposes in the inorganic liquid that recycles, is the problem that presses for solution.All there is this problem in the device of employing hydroxylamine phosphate method prepared hexanolactam at present, also carried out big quantity research in the industry, but all can not thoroughly address this problem.
In " a kind of hydroxylamine phosphate oximation method that prevents prepares the method that azanol decomposes in the inorganic liquid of hexanolactam ", adopt static mixer that the inorganic liquid of different acidity is mixed like Chinese patent notification number CN1091763C, solved hydroxylamine phosphate oximation method and prepared in the caprolactam technology azanol and decompose and cause the whole load of device to reduce, consume the problem that increases.Its weak point is to have increased that facility investment, cost are high, equipment is fragile and complex procedures, does not fundamentally eliminate the factor that azanol decomposes.
Summary of the invention
The present invention is directed to the weak point of prior art, provide that a kind of technology is simple, cost is low, the hydroxylamine phosphate legal system that prevents of energy-conserving and environment-protective is equipped with the method that azanol decomposes in the inorganic liquid of hexanolactam.
In order to solve the problems of the technologies described above; The technical scheme that the present invention adopts is: a kind of method that prevents that in preparing the hexanolactam process azanol decomposes in the inorganic liquid; Above the nitrous gases that the ammonia oxidation and the nitrous gases of preparation hexanolactam device absorbs operation absorbs cat head, adopt mist eliminator to capture nitric acid, the nitric acid that described mist eliminator is captured is introduced at the bottom of the described nitrous gases absorption tower under the reaction solution liquid level.
Further:
Liquid level in the mist eliminator of the present invention is controlled by the inverted U pipe that described mist eliminator liquid phase outlet is provided with automatically;
Inverted U pipe highest point of the present invention is 0.45 ~ 0.65 times of described mist eliminator liquid phase part height;
The position of the mist eliminator described in the present invention is higher 1 ~ 3 meter than top, described nitrous gases absorption tower.
The present invention absorbs the nitric acid that the cat head mist eliminator captures with nitrous gases and introduces under the low reaction liquid liquid level of nitrous gases absorption tower, has so just fundamentally stopped the nitric acid inflow azanol tower intake chute that mist eliminator captures, and makes local H
+Ion is excessive, or nitrous gases leap up into azanol tower intake chute maybe, the azanol that has prevented effectively to cause thus is in the decomposition of azanol tower intake chute.Method technology advantages of simple of the present invention, low, the energy-conserving and environment-protective of cost have fundamentally solved the problem that azanol decomposes in the inorganic liquid that the hydroxylamine phosphate legal system is equipped with hexanolactam, have produced good economic benefit and social benefit.
Description of drawings
Fig. 1 is a process flow sheet of the present invention
As shown in the figure: 1 is the nitrous gases pipeline; 2 is the pipeline of nitrous gases absorption tower to mist eliminator; 3 is mist eliminator; 4 for to go nitrous gases to remove the pipeline of device; 5 is the gas phase pipe; 6 is the inverted U pipe; 7 is nitric acid blanking pipeline; 8 is the nitrous gases absorption tower; 9 is the inorganic process liquor pipeline; 10 is azanol tower intake chute; 11 for removing the reinforced pipeline of azanol tower.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is done to describe in further detail, but the present invention not only is confined to following examples.
Embodiment 1:
Mist eliminator 3 is installed in the over top on nitrous gases absorption tower 8, and the height between mist eliminator 3 and 8 tops, nitrous gases absorption tower is 3 meters; Connect inverted U pipe 6 and nitric acid blanking pipeline 7 to nitrous gases absorption tower 8 bottom reaction solution liquid level upper/lower positions in mist eliminator 3 nitric acid exits.Liquid level in the mist eliminator 3 is controlled by inverted U pipe 6 automatically, and inverted U pipe 6 highest points are 0.5 times of mist eliminator 3 liquid phase part height, and its top connects gas phase pipe 5 and is communicated with mist eliminator 3 gas phases.Nitrous gases (NO by nitrous gases pipeline 1
X) from the bottom feed on nitrous gases absorption tower 8; Absorb the back through the inorganic process liquor of inorganic process liquor pipeline 9 and get into the middle part of mist eliminators 3 from the pipeline 2 of nitrous gases absorption tower to mist eliminator, the nitric acid that captures through mist eliminator 3 is through inverted U pipe 6 and nitric acid blanking pipeline 7 entering nitrous gases absorption towers 8 bottom reaction solution liquid level upper/lower positions; Remove the nitrous gases (NO behind the nitric acid
X) remove device through the pipeline 4 entering nitrous gasess that go nitrous gases to remove device.Absorb nitrous gases (NO
X) after inorganic process liquor after the interchanger heat exchange, get into azanol tower intake chute 10, again through going the reinforced pipeline 11 of azanol tower to remove the azanol synthetic tower.After putting into operation, device thoroughly solved because azanol tower intake chute 11 local H
+Excessive and the nitrous gases (NO of ion
X) scurry into the azanol resolution problem that azanol tower intake chute 11 causes, the azanol decomposing phenomenon does not take place.
Embodiment 2:
Mist eliminator 3 is installed in the over top on nitrous gases absorption tower 8, and the height between mist eliminator 3 and 8 tops, nitrous gases absorption tower is 2 meters; Connect inverted U pipe 6 and nitric acid blanking pipeline 7 to nitrous gases absorption tower 8 bottom reaction solution liquid level upper/lower positions in mist eliminator 3 nitric acid exits.Liquid level in the mist eliminator 3 is controlled by inverted U pipe 6 automatically, and inverted U pipe 6 highest points are 0.55 times of mist eliminator 3 liquid phase part height, and its top connects gas phase pipe 5 and is communicated with mist eliminator 3 gas phases.Nitrous gases (NO by nitrous gases pipeline 1
X) from the bottom feed on nitrous gases absorption tower 8; Absorb the back through the inorganic process liquor of inorganic process liquor pipeline 9 and get into the middle part of mist eliminators 3 from the pipeline 2 of nitrous gases absorption tower to mist eliminator, the nitric acid that captures through mist eliminator 3 is through inverted U pipe 6 and nitric acid blanking pipeline 7 entering nitrous gases absorption towers 8 bottom reaction solution liquid level upper/lower positions; Remove the nitrous gases (NO behind the nitric acid
X) remove device through the pipeline 4 entering nitrous gasess that go nitrous gases to remove device.Absorb nitrous gases (NO
X) after inorganic process liquor after the interchanger heat exchange, get into azanol tower intake chute 10, again through going the reinforced pipeline 11 of azanol tower to remove the azanol synthetic tower.After putting into operation, device thoroughly solved because azanol tower intake chute 11 local H
+Excessive and the nitrous gases (NO of ion
X) scurry into the azanol resolution problem that azanol tower intake chute 11 causes, the azanol decomposing phenomenon does not take place.
Embodiment 3:
Mist eliminator 3 is installed in the over top on nitrous gases absorption tower 8, and the height between mist eliminator 3 and 8 tops, nitrous gases absorption tower is 1 meter; Connect inverted U pipe 6 and nitric acid blanking pipeline 7 to nitrous gases absorption tower 8 bottom reaction solution liquid level upper/lower positions in mist eliminator 3 nitric acid exits.Liquid level in the mist eliminator 3 is controlled by inverted U pipe 6 automatically, and inverted U pipe 6 highest points are 0.58 times of mist eliminator 3 liquid phase part height, and its top connects gas phase pipe 5 and is communicated with mist eliminator 3 gas phases.Nitrous gases (NO by nitrous gases pipeline 1
X) from the bottom feed on nitrous gases absorption tower 8; Absorb the back through the inorganic process liquor of inorganic process liquor pipeline 9 and get into the middle part of mist eliminators 3 from the pipeline 2 of nitrous gases absorption tower to mist eliminator, the nitric acid that captures through mist eliminator 3 is through inverted U pipe 6 and nitric acid blanking pipeline 7 entering nitrous gases absorption towers 8 bottom reaction solution liquid level upper/lower positions; Remove the nitrous gases (NO behind the nitric acid
X) remove device through the pipeline 4 entering nitrous gasess that go nitrous gases to remove device.Absorb nitrous gases (NO
X) after inorganic process liquor after the interchanger heat exchange, get into azanol tower intake chute 10, again through going the reinforced pipeline 11 of azanol tower to remove the azanol synthetic tower.After putting into operation, device thoroughly solved because azanol tower intake chute 11 local H
+Excessive and the nitrous gases (NO of ion
X) scurry into the azanol resolution problem that azanol tower intake chute 11 causes, the azanol decomposing phenomenon does not take place.
Claims (4)
1. method that prevents that in preparing the hexanolactam process azanol in the inorganic liquid from decomposing; Above the nitrous gases that the ammonia oxidation and the nitrous gases of preparation hexanolactam device absorbs operation absorbs cat head, adopt mist eliminator to capture nitric acid, it is characterized in that the nitric acid that described mist eliminator captures is introduced at the bottom of the described nitrous gases absorption tower under the reaction solution liquid level.
2. the method that prevents that in preparing the hexanolactam process azanol decomposes in the inorganic liquid according to claim 1 is characterized in that the liquid level in the described mist eliminator is controlled by the inverted U pipe that described mist eliminator liquid phase outlet is provided with automatically.
3. the method that prevents that in preparing the hexanolactam process azanol decomposes in the inorganic liquid according to claim 2 is characterized in that described inverted U pipe highest point is 0.45 ~ 0.65 times of described mist eliminator liquid phase part height.
4. the method that prevents that in preparing the hexanolactam process azanol decomposes in the inorganic liquid according to claim 1 is characterized in that the position of described mist eliminator is higher 1 ~ 3 meter than top, described nitrous gases absorption tower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101780707A CN102702102A (en) | 2012-05-29 | 2012-05-29 | Method for preventing hydroxylamine in inorganic liquid from decomposing in process of preparing caprolactam |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101780707A CN102702102A (en) | 2012-05-29 | 2012-05-29 | Method for preventing hydroxylamine in inorganic liquid from decomposing in process of preparing caprolactam |
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|---|---|
| CN102702102A true CN102702102A (en) | 2012-10-03 |
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114684792A (en) * | 2020-12-31 | 2022-07-01 | 宁波博汇化工科技股份有限公司 | Sulfur-containing tail gas recovery device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1263090A (en) * | 1998-12-24 | 2000-08-16 | 普拉塞尔技术有限公司 | Method for production of hydroxylammonium phosphate in the synthesis of caprolactam |
| CN1281849A (en) * | 1999-07-26 | 2001-01-31 | 巴陵石化鹰山石油化工厂 | Method for preventing hydroxylamine decomposition in inorganic liquid for manufacturing caprolactam by hydroxylamine phosphate oximation method |
| CN201482372U (en) * | 2009-09-17 | 2010-05-26 | 江西铜业股份有限公司 | Reversed U-shaped sodium sulfide foam catching device |
-
2012
- 2012-05-29 CN CN2012101780707A patent/CN102702102A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1263090A (en) * | 1998-12-24 | 2000-08-16 | 普拉塞尔技术有限公司 | Method for production of hydroxylammonium phosphate in the synthesis of caprolactam |
| US6333411B1 (en) * | 1998-12-24 | 2001-12-25 | Praxair Technology, Inc. | Method for production of hydroxylammonium phosphate in the synthesis of caprolactam |
| CN1281849A (en) * | 1999-07-26 | 2001-01-31 | 巴陵石化鹰山石油化工厂 | Method for preventing hydroxylamine decomposition in inorganic liquid for manufacturing caprolactam by hydroxylamine phosphate oximation method |
| CN201482372U (en) * | 2009-09-17 | 2010-05-26 | 江西铜业股份有限公司 | Reversed U-shaped sodium sulfide foam catching device |
Non-Patent Citations (2)
| Title |
|---|
| 季锦林: "磷酸羟胺法生产己内酰胺工艺中羟胺分解问题的研究", 《化学工业与工程技术》, vol. 25, no. 5, 31 October 2004 (2004-10-31), pages 14 - 15 * |
| 邱时平: "H P O 法经胺及其己内酞胺的工艺特点及操作关键", 《石油化工动态》, no. 7, 31 December 1995 (1995-12-31), pages 17 - 20 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114684792A (en) * | 2020-12-31 | 2022-07-01 | 宁波博汇化工科技股份有限公司 | Sulfur-containing tail gas recovery device |
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Application publication date: 20121003 |